Process for improving the slipping resistance and the delustering of textiles

ABSTRACT

A PROCESS FOR IMPROVING THE SLIPPING RESISTANCE AND THE DELUSTERING OF TEXTILES COMPRISES IMPREGNATING TEXTILES WITH ORGANIC SOLUTIONS CONTAINING REACTION PRODUCTS OF ALCOHOLATES OF ZIRCONIUM, TITANIUM OR ALUMINUM WITH ALIPHATIC, SATURATED 1- OR 2-VALENT ALCOHOLS WITH 2 TO 6 CARBON ATOMS, OR WITH MONOALKYL ETHERS OF THESE 2-VALENT ALCOHOLS, WHEREBY THESE MONOALKYL ETHERS HAVE TOTALLY 4 TO 8 CARBON ATOMS, WITH PARAFORMALDEHYDE IN A MOL RATIO OF 1:1 TO 1:10 AND POSSIBLY 0.06 TO 1 MOL METAL SALTS DERIVED FROM FATTY ACIDS WITH 6 TO 18 CARBON ATOMS WITH 2VALENT METALS PER MOL ALCOHOLATE AS STABILIZERS. THEN THE SUPERFLUOUS SOLUTION IS REMOVED AND THE TEXTILES ARE DRIED. THE INVENTION IS PARTICULARLY CHARACTERIZED IN THAT THE REACTION PRODUCTS ARE DERIVED FROM SUCH ALCOHOLATES OF ZIRCONIUM, TITANIUM OR ALUMINUM WHEREIN 0.5 TO 2.5 EQUIVALENTS OF ALCOHOL RESIDUES ARE REPLACED BY RESIDUES OF LOW SATURATED AND/OR UNSATURATED CARBOXYLIC ACIDS WITH 2 TO 4 CARBON ATOMS.

United States Patent 3,730,762 PROCESS FOR IMPROVING THE SLIPPING RESISTANCE AND THE DELUSTERING 0F TEXTILES Hans Deiner, Neusas, near Augsburg, and Heinrich Singer, Horgau, near Augsburg, Germany, assignors to Chemische Fabrik Pfersee GmbH., Augsburg, Germany No Drawing. Filed May 18, 1971, Ser. No. 144,624 Claims priority, application Germany, June 30, 1970, P 20 32 387.9; July 7, 1970,P 20 33 523.3 Int. Cl. D06m 15/00 US. Cl. 117139.5 CQ Claims ABSTRACT OF THE DISCLOSURE A process for improving the slipping resistance and the delustering of textiles comprises impregnating textiles with organic solutions containing reaction products of alcoholates of zirconium, titanium or aluminum with aliphatic, saturated lor 2-valent alcohols with 2 to 6 carbon atoms, or with monoalkyl ethers of these 2-valent alcohols, whereby these monoalkyl ethers have totally 4 to 8 carbon atoms, with paraformaldehyde in a mol ratio of 1:1 to 1:10 and possibly 0.06 to 1 mol metal salts derived from fatty acids with 6 to 18 carbon atoms with 2- valent metals per mol alcoholate as stabilizers. Then the superfluous solution is removed and the textiles are dried. The invention is particularly characterized in that the reaction products are derived from such alcoholates of zirconium, titanium or aluminum wherein 0.5 to 2.5 equivalents of alcohol residues are replaced by residues of low saturated and/or unsaturated carboxylic acids with 2 to 4 carbon atoms.

This invention relates to a process for improving the slipping resistance and the delustering of textiles.

A prior art process for improving the slipping resistance and the delustering of textiles consists in that textiles are impregnated with organic solutions containing reaction products of alcoholates of zirconium, titanium or aluminum with aliphatic saturated, 1- or 2-valent alcohols with 2 to 6 carbon atoms, or with moonalkyl ethers of these 2-valent alcohols, whereby these monoalkyl ethers have totally 4 to 8 carbon atoms, with paraformaldehyde in a mol ratio of 1:1 to 1:10. The superfluous solution is then removed and the textiles are dried. Good results are produced when the organic solutions besides the reaction products have 0.06 to 1 mol metal salts derived from fatty acids with 6 to 18 carbon atoms with 2-valent metals, particularly zinc, tin and magnesium, per mol alcoholate as stabilizers. Examples of such metal soaps are Al-, Zn-, Sn-octoate; Ba-, Ca-, Mn-oleate; Mg-, Ca-laurate and Sn-, Zr1-, Mg-stearate.

However, when working conditions are unsatisfactory, products introduced into this process will have an insufficient hydrolytic stability which results in unstable treating baths and thus possibly in the formation of spots upon the treated goods.

An object of the present invention is to eliminate these drawbacks.

Other objects of the present invention will become apparent in the course of the following specification.

In the accomplishment of the objectives of the present invention it was found desirable to use for the making of reaction products such alcoholates of zirconium, tita- 3,730,762 Patented May 1, 1973 nium or aluminum wherein 0.5 to 2.5, specifically 1 to 2, equivalents of alcohol residues are replaced by low, saturated and/or unsaturated carboxylic acids with 2 to 4 carbon atoms. The surprising effect is that this greatly improves hydrolytic stability without spoiling the splitting resistance and the delustering effects.

As low, saturated and/or unsaturated carboxylic acids with 2 to 4 carbon atoms can be used acrylic acid, crotonic acid, acetic acid or propionic acid; acrylic acid and acetic acid are preferred.

Preferably, the manufacture of the condensation products introduced into the process of the present invention is carried out by reacting one mol of an aloholate of zirconium, titanium or aluminum with 0.5 to 2.5 mols of a low, saturated and/or unsaturated carbonic acid, after the end of the exothermic reaction heating it at return flow for about 10 to 30 minutes and possibly distilling off the freed alcohol. Thereupon these alcoholates are further reacted in known manner with paraformaldehyde to produce useable products.

Alcoholates of zirconium, titanium and aluminum used as initial substances are derived from lor 2-valent saturated aliphatic alcohols with 2 to 6 carbon atoms or from monoalkyl ethers of these 2-valent alcohols, whereby these monoalkyl ethers have a total of 4 to 8 carbon atoms. Examples of such alcoholates are: alcoholates of zirconium and titanium with n-propanol, iso-propanol, nbutanol, iso-butanol, n-amyl alcohol, popandiol (1,2), butandiol (1,4), or butandiol-(1,3), glycolmonobutyl ether, glycolmonohexyl ether, respectively the alcoholates of aluminum with propandiol-(1,2), butandiol-(1,4) and others, glycolmonobutyl ether, Z-methyl pentane diol-(Z, 4), and propylene glycol-n-butyl ether. Particularly suitable are such alcoholates of zirconium, titanium and aluminum, which are derived from low aliphatic, saturated, monovalent alcohols. The preferred ratio of carbonic acid residues per mol zirconium-, titanium-and/or aluminum-alcoholate lies specifically at l to 2 equivalents.

Reaction products which, as is also known, can be further stabilized with metal salts, are well soluble in benzine or chlorated hydrocarbons and are used, depending upon type or material and the use, in amounts of 12 to 50 gr./l. of an approximately 40% solution. To provide good slipping resistance 12 to 25 gr./l. and for delustering 25 to 50 gr./l. of the reaction products are introduced. After removal of the solvent ordinary drying at a temperature of to 110 C. produces the delustering eifect and the slipping resistance. In case of woolen textiles the fixing is also possible by a short decatizing.

According to a special embodiment of the process of the present invention it was found that the slipping resistance can be further improved to a considerable extent it colloidal SiO tis added to the products. This addition preferably takes place in the presence of up to 330 percent by weight, particularly -260 percent by weight, of a low monovalent alcohol, related to reaction products of metal alcoholate and paraformaldehyde. Then the alcohol specifically prevents the concentrated products from becoming too thick. Furthermore, products containing alcohol produce more stable baths. The low alcohol is preferably introduced in water free form to avoid hydrolysis. As low monovalent alcohols can be named ethanol, propanol and i-butanol.

It was found surprisingly that the combination of the present invention of reaction products with the colloidal SiO produces stable baths which have no tendency to redimentation and opalesce only weakly. A further important advantage of the process of the present invention consist in that the effects of slipping resistance thereby produced are not only resistant to chemical cleaning but are resistant to a great extent to washing.

As colloidal SiO particularly used SiO produced from SiCl by thermic decomposition which in addition to having a very small and uniform grain size has a large outer surface and is amorphous. It is particularly advantageous to use a SiO the grain size of which is less than 40 millimicrons, particularly less than 16 millirnicrons and which has an outer surface of about 200 sq. m. per gr.

The amount of SiO man be 15 to 150% particularly 40 to 80%, related to the weight of the reaction product from metal alcoholate and paraformaldehyde. However, the lower limit is not critical since obviously products with a lower amount of SiO can be also effectively used.

According to a special embodiment of the process of the present invention the treating baths are produced by diluting with chlorated hydrocarbon or benzine the concentrated products which contain the reaction products produced as described above, the colloidal Si and in addition to chlorated hydrocarbon or benzine possibly a water-free low monovalent alcohol, for example, ethanol, or propanol, to produce a useable concentration. Then the manufacture of concentrated products takes place by diluting if necessary the concentrated solutions of the reaction products obtained as above described, with a further solvent and possibly adding the above-mentioned alcohol, whereupon the colloidal Si0 is worked in under forceful stirring. Thus a solution is obtained containing advantageously about 20% solid substance.

Depending upon the desired effect the treating baths should contain between 4 gr. to 16 gr. per liter of the solid substance, i.e. the sum of reaction product plus metal soaps plus colloidal SiO To produce delustering effects it is advisable to increase the solid content of the treating bath per liter to 20 to 30 gr. The process is carried out in a simple manner in that the treated textiles are impregnated with the baths, then are freed from excessive bath by squeezing, swinging or suction and are then dried.

If textile are treated with baths which contain only the colloidal Si0 in chlorated hydrocarbon or benzine, then inequalities are produced, since the colloidal SiO strongly sediments in these treating baths. Surprisingly the baths used in accordance with the present invention show no sedimentation of SiO but are only lightly opal. Furthermore, it is surprising that the combination of reaction products used in accordance with the present invention and the colloidal SiO makes it possible to produce a slipping resistance which greatly resists washing.

This treatment can be applied to fabrics of cellulose fibers or regenerated cellulose fibers, particularly cellulose ester fibers, but also to fully synthetic fabrics or mixed fabrics with different types of fibers.

Devices suitable for carrying out the process of the present invention are so-called continuous devices which have been constructed for treating metered goods with organic solvents according to the foularding principle. However, machines employed in chemical cleaning for subsequent impregnation of clothing can be also used.

The produced reaction products can be advantageously combined with other known textile refining agents soluble in organic solvents. Thus jointly with silicons, parafiin and artificial resins a slipping resistance and also a good hydrophobic effect are produced. Furthermore, a combination with finishing agents and softeners is possible.

Reaction products useable for the delustering and for providing slipping resistance can be manufactured as follows:

(a1) 12 gr. acrylic acid are slowly added to 54 gr. of 100% zirconium tetra-n-propylate, then they are heated to return flow and stirred for 15 min. at return flow. Then the formed alcohol (about 10 gr.) is distilled off and thereupon the temperature of the product is 4 allowed to sink to 60 C. while stirring. Then are added gr. n-propanol, 30 gr. paraformaldehyde and 15 gr. zinc octoate and the mixture thus produced is heated again for 15 min. while stirring and refluxing. Then it is cooled and diluted with 51 gr. tetrachlorethylene to a clear solution.

(a2) From gr. of a 50% titanium tetra-n-propylate solution in propanol, n-propanol is initially distilled off in vacuum at up to 90 C., then while stirring 24 gr. acrylic acid are slowly added, the mixture is heated to reflux and left therefor about 20 min. Then the formed alcohol is distilled off and after that the temperature of the product is lowered to about 60 C. while stirring. Then 80 gr. n-propanol and 10 gr. paraformaldehyde are added and the mixture is heated while stirring up to C., so that the alcohol is practically substantially distilled off. The mixture is cooled to about 80 C., 15 gr. magnesium stearate in gr. tetrachlorethylene are added and then it is stirred for 5 minutes at this temperature.

(a3) 118 gr. of pure aluminum triisobutylate are stirred with 2 mols Water-free butandiol-(1,4) and are heated to 95 C. until a clear solution is produced. Then the formed isobutyl alcohol is distilled off in vacuum at a temperature of up to 110 C. Slowly 45 gr. acrylic acid are added and the mixture is heated for 15 minutes under stirring and refluxing. Thereupon the freed alcohol is again distilled off and the produced mixture is cooled to about 55 C. Then 30 gr. paraformaldehyde and 80 gr. tin-octoate are added, the mixture is heated up to C. at return flow and then diluted with tetrachlorethylene to a 25% solution.

(a4) The solvent is distilled off in vacuum from 75 gr. of a 72% solution of zirconium tetra-n-propylate with propanol, then slowly 10 gr. acetic acid are added and the mixture is heated for 25 min. at reflux. After distilling off the alcohol which was then formed, the temperature of the product is allowed to sink while stirring to about 60 C., then 70 gr. n-propanol, 25 gr. paraformaldehyde and 51 gr. tetrachlorethylene are added and this mixture is heated once again for 15 min. at reflux. After cooling a clear product solution is produced which can be diluted with tetrachlorethylene in any ratio.

(a5) The product produced under (a4) will be still more resistant against hydrolysis if 20 gr. zinc laurate are added along with propanol, paraformaldehyde and tetrachlorethylene.

Concentrated products used according to the special embodiment of the present invention are produced as follows:

(bl) 20 gr. of a reaction product produced as described in (a1) are dissolved in a mixture of 12 gr. water-free propanol and 30 gr. tetrachlorethylene and 5 gr. silicon dioxide (size of particles about 30 millimicrons, surface about sq. m./gr.) are worked in by means of a rapid stirrer. The product thus obtained is an opal solution and can be diluted without any separations.

(b2) 24 gr. of the product solution prepared as described in (a2) are diluted with 56 gr. tetrachlorethylene and 10 gr. silicon dioxide (size of particles about 10 millimicrons, surface about 280 sq. m./gr.), are worked in with forceful stirring. The opal product thus produced after dilution is very well suitable for delustering and improving slipping resistance.

A product obtained by adding 11 gr. n-propanol prior to the addition of SiO produces more permanent baths.

(b3) To 40 gr. of the solution prepared as described in (a3) are added 10 gr. water-free ethanol and into this solution are worked in with forceful stirring 3 gr. of silicon dioxide described in detail in (b1). An opal solution is produced which can be easily diluted with chlorated hydrocarbons.

(b4) 20 gr. of the product solution prepared as described in (a4) are reacted with 60 gr. of a solvent mixture (trichlorethylene to propanol 3:1) and then 15 gr. of silicon dioxide described in detail in (b2) are stirred in EXAMPLE 1 25 gr. of a product solution obtained according to requirements stated in (al) are filled with tetrachlorethylcue to 1 liter. A viscose lining cloth (twill) was foularded with this bath, pressed to 120% bath reception and dried at 100 C. A very well delusted cloth is produced having an excellent slipping resistance.

EXAMPLE 2 45 gr. of a product solution obtained according to requirements stated in (a2) are filled with trichlorethylene to 1 liter. This solution was used for foularding a polyester fabric (georgette) which was then pressed to 80% bath reception and dried at 100 C. A fabric is produced having good slipping resistance which at the same time is very well delustered.

EXAMPLE 3 45 gr. of a melamine resin produced according to EX- ample 1 of the Austrian Pat. No. 223,579 and 70 gr. of the product solution obtained according to requirements stated in (a3) are dissolved in trichlorethylene and filled to 1 liter. This bath was used for foularding an acetate lining taffeta. The fabric was pressed to 100% bath reception and dried at 80 C. The sample thus produced is very well delustered and resistant against slipping with good water drop fastness.

EXAMPLE 4 50 gr. of a 50% solution of hydrogenmethyland dimethylpolysiloxane 1:1 in tetrachlorethylene are mixed with 18 gr. of the product solution obtained according to requirements stated in (a5) and are filled with tetrachlorethylene to 1 liter. This bath was used to impregnatea viscose lining which was then pressed to 120% bath reception and dried at 100 C. The fabric thus treated has good slipping resistance and at the same time good water repellancy.

EXAMPLE 6 100 gr. of the product solution obtained according to requirements stated in (b1) are filled with tetrachlorethylene to 1 liter. This bath was used for foularding a viscose lining cloth (twill), which was then pressed to 120% bath reception and dried at 100 C. A fabric is produced which is very well delustered and has an exceptionally good slipping resistance.

EXAMPLE 7 140 gr. of the product solution obtained according to requirements stated in (b2) are filled with trichlorethylene to 1 liter. This solution was used for foularding a polyester fabric (georgette), which was pressed to 80% bath reception and then dried at 100 C. A fabric is produced which has very good slipping resistance and at the same time is excellently delustered.

EXAMPLE 8 45 gr. of a melamine resin produced according to Example 1 of the Austrian patent No. 223,573 and 100 gr. of the product solution obtained according to the requirements stated in (b3) are dissolved in trichlorethylene and filled to 1 liter. This bath was used to foulard an acetate lining tatfety which was then pressed to 100% bath reception and dried at C. The sample thus produced is excellently delustered and slipping resistant with good water drop fastness.

EXAMPLE 9 A bath used to impregnate a polyester fabric (georgette) consisted of 75 gr. of a 30% solution of a postchlorated polyvinylchloride in a mixture of 60* parts tetrachlorethylene and 10 parts butyl acetate and 30* gr. of the product solution obtained according to the requirements stated in (b4) filled to 1 liter by tetrachlorethylene. The fabric was pressed to 80% bath reception and dried at C. The fabric has very good slipping resistance and at the same time has a good handle finish.

EXAMPLE 10 50 gr./l. of a 50% solution of hydrogenmethyland dimethylpolysiloxanes 1:1 in tetrachloroethylene and 30 gr. of a product solution obtained according to the requirements stated in (b5) are mixed and are filled with tetrachloroethylene to 1 liter. This bath was used to impregnate a viscose lining which was then pressed to bath reception and dried at 100 C. The fabric thus treated has a very good slipping resistance and at the same time good water repellancy.

We claim:

1. In a process for making textiles slipping resistant and delustered, which comprises impregnating the textile with organic solutions having reaction products of alcoholates of zirconium, titanium or aluminum with aliphatic saturated 1- or 2-valent alcohols with 2 to 6 carbon atoms or with monoalkyl ethers of these 2-valent alcohols, whereby these monoalkyl ethers have totally 4 to 8 carbon atoms, with paraformaldehyde in a mole ratio 1:1 to 1:10, then removing superfluous solution from the textile and drying it, the improvement which consists in that the reaction products are derived from such alcoholates of zirconium, titanium or aluminum wherein 0.5 to 2.5 equivalents of alcohol residues are replaced by residues of low, saturated or unsaturated carboxylic acids with 2 to 4 carbon atoms.

2. The process in accordance with claim 1, comprising the use of reaction products of zirconium alcoholates of monovalent, aliphatic, saturated. alcohols wherein 1 to 2 equivalents of alcohol residues are replaced by acrylic acid or acetic acid residues.

3. The process in accordance with claim 1, comprising treating the textile with an organic bath which in addition to said reaction products contains colloidal SiO removing superfluous bath after the treatment and then drying the textile.

4. The process in accordance with claim 3, wherein the bath contains from 15% to colloidal SiO related to the weight of the reaction product of metal alcoholate and paraformaldehyde.

5. The process in accordance with claim 3, wherein the colloidal Si0 has a grain size less than 40 millimicrons.

6. The process in accordance with claim 1, wherein said bath contains up to 330 parts by weight of a low, monovalent alcohol related to the weight of the reaction product of metal alcoholate and paraformaldehyde.

7. The process in accordance with claim 3, comprising treating the textile with an organic bath which in addition contains a low monovalent alcohol.

8. The process in accordance with claim 1, comprising References Cited treating the textile with an organic bath which in addition contains 0.06 to 1 mol metal salts derived from fatty acids UNITED STATES PATENTS with 6 to 18 carbon atoms with 2-valent metals per mol 2,801,190 7/1957 Orthner at a] 117135-5 alcoholate as stabilizers 5 2,527,329 10/1950 Powers et al. 1l7139.5 CF 9. The process in accordance with claim 5, wherein 1,906,149 4/1933 Gardner 117-4445 tchgniolloidal SiO has a grain size less than 16 millimi- MURRAY K ATZ Primary Examiner 10. The process in accordance with claim 6, wherein DAVIS, Assistant Examiner the bath contains 100 to 260 parts by weight of a low, 10 U S Cl X R monovalent alcohol related to the weight of the reaction product of metal alcoholate and paraformaldehyde. 1l7138.8 F, 139.5 CF, 141, 144, 161 L 

